Abstract:We report thermo-mechanically responsive and thermochromic behavior in the single crystalline organic semiconductor butoxyphenyl N-substituted naphthalene diimide (BNDI). We show that initially monoclinic single crystals of BNDI undergo a single-crystal to single-crystal transition to a triclinic phase. This transition accompanies large changes in the crystal packing, a visible decrease in crystal size, reversible thermochromic behavior, and motion including bending, jumping, and splitting. We have shown that … Show more
“…The difference in these transition enthalpies supports that enol-keto photoisomerization triggers the phase transition β → γ, but does not trigger the phase transition α → β due to a larger enthalpy. The enthalpy at the phase transition β → γ is also smaller than other structural phase transitions of molecular crystals 18,21,24,30,[33][34][35] .…”
Structural phase transitions induced by external stimuli such as temperature, pressure, electromagnetic fields, and light play crucial roles in controlling the functions of solid-state materials. Here we report a new phase transition, referred to as the photo-triggered phase transition, of a photochromic chiral salicylideneamine crystal. The crystal, which exhibits a thermal single-crystal-to-single-crystal phase transition which is reversible upon heating and cooling, transforms to the identical phase upon light irradiation at temperatures lower than the thermal transition temperature. The photo-triggered phase transition originates from the strain of trans-keto molecules produced by enol-keto photoisomerization owing to the small energy barrier associated with changes in the crystal structure. The photo-triggered phase is metastable and returns to the initial stable phase via back isomerization from the trans-keto to enol form.
“…The difference in these transition enthalpies supports that enol-keto photoisomerization triggers the phase transition β → γ, but does not trigger the phase transition α → β due to a larger enthalpy. The enthalpy at the phase transition β → γ is also smaller than other structural phase transitions of molecular crystals 18,21,24,30,[33][34][35] .…”
Structural phase transitions induced by external stimuli such as temperature, pressure, electromagnetic fields, and light play crucial roles in controlling the functions of solid-state materials. Here we report a new phase transition, referred to as the photo-triggered phase transition, of a photochromic chiral salicylideneamine crystal. The crystal, which exhibits a thermal single-crystal-to-single-crystal phase transition which is reversible upon heating and cooling, transforms to the identical phase upon light irradiation at temperatures lower than the thermal transition temperature. The photo-triggered phase transition originates from the strain of trans-keto molecules produced by enol-keto photoisomerization owing to the small energy barrier associated with changes in the crystal structure. The photo-triggered phase is metastable and returns to the initial stable phase via back isomerization from the trans-keto to enol form.
“…This includes the development of Gd-hydroxypyridonate-modified MS2 nanoparticles, 14,15 Gd-1,4,7,10-tetraaza-cyclododecane-1,4,7,10-tetraacetic acid (DOTA)loaded cowpea mosaic virus (CPMV) nanoparticles, 16 as well as metal-free tobacco mosaic virus (TMV) with paramagnetic organic radical compounds. 17 Ideally, multifunctional contrast agents should be suitable for both near-infrared fluorescence (NIRF) imaging and ultrahigh field magnetic resonance imaging (UHFMRI) because these techniques work well in combination. 12,18 The imaging reagents in each case are nonionizing, and a single nanoparticle featuring such contrast agents would achieve high sensitivity, deep tissue penetration, and high spatial resolution, making them suitable for multiscale scanning from the cellular level to the organ.…”
One of the greatest challenges in nanomedicine is the low efficiency with which nanoparticles are delivered to lesions such as tumors in vivo. Here, we show that Physalis mottle virus (PhMV)-like nanoparticles can be developed as bimodal contrast agents to achieve long circulation, specific targeting capability, and efficient delivery to tumors in vivo. The self-assembling coat protein nanostructure offers various opportunities to modify the internal and external surfaces separately. After loading the internal cavity of the particles with the fluorescent dye Cy5.5 and paramagnetic Gd(III) complexes, we modified the outer surface by PEGylation and conjugation with targeting peptides. Using this combined approach, we were able to monitor a human prostate tumor model for up to 10 days by near-infrared fluorescence and magnetic resonance imaging, with up to 6% of the injection dose remaining. Our results show that PhMV-like nanoparticles provide a promising and innovative platform for the development of next-generation diagnostic and therapeutic agents.
“…17 As an approach of engineered science, researchers have studied the mechanism for the color change with temperature based on the relationship between structure and properties. 18,19 For example, Dharmarwardana et al 20 explored the thermochromic behavior of organic single crystal (SC) butoxyphenyl N-substituted naphthalene diimide (BNDI, Figure 4a) and found that the yellow monoclinic polymorph (α-phase, Figure 4b) BNDI underwent a reversible thermochromic structural transition to the triclinic polymorph (β-phase) upon heating, and subsequently changed to orange crystals after cooling down to room temperature (Figure 4c). They believed that this thermochromic behavior was based on the phase transition from a thermo-mechanical responsive SC-to-SC change (Figure 4d).…”
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